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Abstract:

A process for producing a polymer, characterized in that a polymer having
juts is produced by carrying out photopolymerization of at least one
photopolymerizable polymerization precursor containing a photocurable
compound having two or more unsaturated bonds by irradiation with active
energy ray, optionally in the presence of at least one additive component
for adding a polymer function, in a supercritical fluid or subcritical
fluid; and a polymer having juts of 10 nm or more height, which height is
0.1-fold or more of the diameter of the juts, produced by the above
process.

Claims:

1. A process for producing a polymer, which comprises a step of carrying
out photopolymerization of at least one photopolymerizable polymerization
precursor containing a photocurable compound having two or more
unsaturated bonds by irradiation with active energy ray in a
supercritical fluid or subcritical fluid to produce a polymer having
juts.

2. The process for producing a polymer according to claim 1, wherein the
supercritical fluid or subcritical fluid is supercritical carbon dioxide
or subcritical carbon dioxide.

3. The process for producing a polymer according to claim 1, wherein the
polymer having juts is formed on an active energy ray-permeable base
material so disposed as to be exposed to the supercritical fluid or
subcritical fluid.

4. The process for producing a polymer according to claim 3, wherein the
active energy ray-permeable base material is so disposed that an incident
surface for active energy ray of the base material is not exposed to the
supercritical fluid nor subcritical fluid, and the exiting surface for
active energy ray of the base material is exposed to the supercritical
fluid or subcritical fluid, and,the photopolymerization of at least one
photopolymerizable polymerization precursor containing the photocurable
compound having two or more unsaturated bonds is carried out by
irradiation with active energy ray while permeating through the active
energy ray-permeable base material to form the polymer having juts on the
exiting surface for active energy ray of the active energy ray-permeable
base material.

5. The process for producing a polymer according to claim 4, wherein the
irradiation with active energy ray onto the active energy ray-permeable
base material is conducted via a mask pattern to selectively form the
polymer having juts on a part of the exiting surface for active energy
ray of the active energy ray-permeable base material wherein the active
energy ray was permeated through the part.

6. A process for producing a polymer, which comprises a step of carrying
out photopolymerization of at least one photopolymerizable polymerization
precursor containing a photocurable compound having two or more
unsaturated bonds by irradiation with active energy ray in a
supercritical fluid or subcritical fluid in the presence of at least one
additive component for adding a polymer function to produce a polymer
having juts containing the additive component.

7. The process for producing a polymer according to claim 6, wherein the
additive component is at least one organometal complex.

8. The process for producing a polymer according to claim 7, wherein the
additive component is at least one organoplatinum complex.

9. A polymer having juts wherein the height of juts is 0.1-fold or more of
the diameter of the juts and the height of juts is 10 nm or more.

10. The polymer according to claim 9, wherein the height of juts is 1-fold
or more of the diameter of the juts.

11. The polymer according to claim 9, wherein the height of juts is 1
μm or more.

12. The polymer according to claim 9, which has a water-repellant
function.

13. The polymer having juts according to claim 12, wherein the contact
angle with water is 90.degree. or more.

14. A structure containing the polymer having juts according to claim 9 on
a base material.

15. A polymer having juts, which contains at least one additive component
for adding a polymer function.

16. The polymer according to claim 15, wherein the height of juts is
0.1-fold or more of the diameter of the juts and the height of juts is 10
nm or more.

17. A structure containing the polymer having juts according to claim 15
on a base material.

18. The polymer according to claim 15, wherein the additive component is
at least one organometal complex.

19. A polymer having juts and containing a metal and/or metal oxide, which
was produced by reducing treatment of the polymer having juts according
to claim 18.

20. A membrane containing a metal and/or metal oxide as a main component,
which was produced by calcining treatment of the polymer having juts
according to claim 18.

Description:

TECHNICAL FIELD

[0001]The present invention relates to a polymer having juts (including
also a so-called polymer brush) and a process for producing a polymer
having juts, using a supercritical fluid or subcritical fluid. Further,
the present invention relates to a structure containing a polymer having
juts on a base material.

BACKGROUND ART

[0002]Recently, because of its peculiar shape, a polymer brush is paid to
attention. The polymer brush has a structure in which a polymer chain of
which end is fixed (by chemical bond or adsorption) to the surface of
solid is extended along a direction vertical to the surface of solid. The
degree of extending of a polymer chain depends significantly on graft
density.

[0003]The polymer brush is obtained usually by grafting a polymer chain to
the surface of solid by surface graft polymerization, particularly,
surface initiation living radical polymerization.

[0004]For example, Japanese Patent Application Laid-Open (JP-A) No.
2001-131208 discloses a process of preparing a polymerizable brush base
material comprising a process of providing a base material carrying at
least one covalently bonded free radical initiator having a radical
generating portion at a position distant from the base material, and a
process of contacting the covalently bonded base material with a monomer,
under conditions of promoting free radical polymerization from the
radical generating portion of the initiator, to form a polymerizable
brush.

[0005]JP-A No. 2002-145971 describes a process for producing a polymer
brush by surface initiation living radical polymerization. The surface
initiation living radical polymerization is specifically a method in
which, first, a polymerization initiator is fixed by a Langmuir-Blodgett
(LB) method or a chemical adsorption method to the surface of solid,
then, a polymer chain (graft chain) is grown on the surface of solid by
living radical polymerization (ATRP method). This publication describes
that growth of a polymer chain of regulated length and length
distribution on the surface of a substrate at high surface density
conventionally not found is made possible by surface initiation living
radical polymerization, and due to its high graft density, membrane
thickness matching even elongated chain length is obtained by swelling
with a solvent, realizing a condition of "polymer brush" in the true
sense for the first time. This publication also describes that in
conventional radical polymerization by surface initiation, a radical once
generated grows until irreversible stopping to generate graft chains
sequentially, thereby preventing adjacent grafting because of steric
hindrance of a previously grown graft chain, while in this system,
polymerization progresses in living mode, namely, all graft chains grow
approximately evenly, thereby, steric hindrance between adjacent graft
chains is decreased and, this is believed to be a factor for obtaining
high graft density.

[0006]The above-mentioned JP-A No. 2002-145971 discloses a nano structure
functional body characterized in that graft polymer chains constituting a
graft polymer layer disposed on the surface of a substrate by graft
polymerization obtained by such surface initiation living radical
polymerization has a structure multi-layered in chemical composition
along membrane thickness direction by copolymerization with other
monomers or oligomers. Further, this publication discloses also a nano
structure functional body characterized in that a polymerization
initiation portion (polymerization initiation moiety) of molecules
disposed on the surface of a substrate is inactivated in given pattern
along membrane surface direction, then, a polymerization initiation
portion not inactivated is graft-polymerized to give a graft polymer
layer disposed in given pattern.

[0013]Japanese Patent Application National Publication (Laid-Open) No.
2002-535450 describes application of a polymer brush to a nucleic acid
molecule detecting method (DNA sensor and the like) and a method of
purifying a compound such as nucleic acids, (poly)saccharides or
(poly)peptides, or their complexes, antibodies and the like from a
sample. Further, the above-mentioned publication describes also use of a
polymer brush as an affinity matrix, its use as a sensor chip, its use
for fixing of an initiation molecule for formation of an oligomer or
polymer, preferably, for synthesis of a nucleic acid or peptide, and its
use as a gel in separation of molecules, preferably, organism molecules,
in electric field.

[0014]Though differing from a polymer brush, A. K. GEIM et al.,
"Microfabricated adhesive mimicking gecko food-hair", Nature materials,
Vol. 2, July 2003, p. 461-463 describes a high density array of a
polyimide in the form of pyramid (hair). Specifically, a polyimide film
having a thickness of 5 μm is formed on a silicon base plate, and an
aluminum pattern is transferred to the polyimide film by oxygen plasma
etching using an aluminum mask, to form, for example, a polyimide array
in the form of pyramid having a diameter of 0.6 μm and a height of 2.0
μm. This publication describes also that this has high stickiness.

[0015]These conventional polymer brushes are capable of having a structure
of maximum elongation of a polymer chain (graft chain) only in a good
solvent, and under dry condition or in a poor solvent, have a structure
of a fallen or folded polymer chain (graft chain).

[0016]The supercritical fluid is a fluid of which density is near that of
liquid and of which viscosity and diffusion coefficient are near those of
gas, and has diffusibility of gas and substance dissolvability of liquid,
together. That is, the supercritical fluid has various effects as a
reaction solvent.

[0017]Conventionally, the supercritical fluid is utilized for separation
by extraction of active ingredients, removal by extraction of unnecessary
components, and the like such as extraction of hop extracts and
aromatics, decaffeination from coffee and tobacco, and the like. For
example, production of caffeine-less coffee utilizing supercritical
carbon dioxide has been industrially carried out from approximately the
latter half of the 1970's.

[0018]Recently, the supercritical fluid is utilized also for removal and
concentration of impurities such as chemical raw materials, products and
the like such as removal of unreacted monomers from a polymer,
concentration and dehydration of alcohol, and the like. Further, the
supercritical fluid is utilized also for de-bindering of ceramics,
washing and drying of semiconductors and machine parts, and the like. For
example, JP-A No. 7-149721 discloses a method of purifying a bismaleimide
compound characterized in that an ether imide-based bismaleimide compound
containing impurities such as aromatic hydrocarbon solvents and the like
used in production is subjected to impurity extraction removal treatment
of contacting with carbon dioxide under supercritical condition including
a pressure of 60 atom or more and a temperature of 20° C. or
higher or under condition near the supercritical condition.

[0019]Additionally, the supercritical fluid is utilized for fine particle
formation, thin film formation and fine fiber formation by rapid
expansion (RESS method) such as production of barba-like fine particles
such as silica and the like, and also for fine particle formation and
thin film formation by poor solvent achievement (GAS method) such as
reinforcement (surface coating) of silica aero gel, and the like. For
exampIe, JP-A No. 8-104830 discloses a method of producing a fine
particle for paint characterized in that a polymer polymerization
reaction solution in a polymerization process for producing a polymer
solid raw material for paint is dissolved in a supercritical phase using
carbon dioxide and a polar organic solvent, and expanded rapidly.

[0020]Conventionally, polymers such as a fine particle for paint, and the
like are produced by a solution polymerization method using a large
amount of organic solvent, and the like from the standpoints of control
of polymerization reaction speed, handling of a polymerization product,
and the like. However, in the solution polymerization method, a polymer
is produced in solution condition containing a solvent approximately in
half amount, thus, a de-solventing process is necessary of removing a
solvent from the resulting polymer solution and drying the polymer, after
polymerization, leading to a complicated process. Treatment of an organic
solvent vaporizing in the de-solventing process is also problematical.

[0021]In contrast, recently, there is a trial for producing a polymer
using as a solvent a supercritical fluid, particularly, supercritical
carbon dioxide. When supercritical carbon dioxide is used as a solvent,
there is no necessity to effect removal of solvent and drying after
polymerization, therefore, the process can be simplified and cost can be
decreased. From the standpoint of no use of an organic solvent,
environmental load is also small. Additionally, carbon dioxide can be
easily recovered and recycled as compared with an organic solvent.
Further, in many cases, there is a difference in solubility in carbon
dioxide between a polymer and a monomer. As a result, when supercritical
carbon dioxide is used as a solvent, the amount of unreacted monomers
contained in a product polymer lowers, thus, a polymer of higher purity
can be produced.

[0022]Regarding a method of producing a polymer using a supercritical
fluid, Japanese Patent Application National Publication (Laid-Open) No.
7-505429, for example, discloses a method of producing a fluoro polymer
containing a process of solubilizing a fluoro monomer in a solvent
containing supercritical carbon dioxide and a process of thermally
polymerizing a fluoro monomer in the solvent in the presence of a radical
polymerization initiator, to produce a fluoro polymer.

[0023]JP-A No. 2000-26509 discloses a method of producing a fluoro polymer
in which at least one fluorinated monomer is thermally polymerized in
supercritical carbon dioxide using dimethyl(2,2'-azobisisobutyrate) as an
initiator.

[0024]JP-A No. 2002-327003 discloses a method of producing a fluorinated
alkyl group-containing polymer in which a radical-polymerizable monomer
component containing a fluorinated alkyl group-containing (meth)acrylate
in an amount of 20 wt % or more is thermally polymerized using
supercritical carbon dioxide as a polymerization solvent.

[0025]JP-A No. 2001-151802 discloses a method of producing a polymer fine
powder in which a monomer composition containing an ethylenically
unsaturated monomer having a carboxyl group such as (meth)acrylic acid
and the like is thermally radical-polymerized in supercritical carbon
dioxide to give a polymer fine powder.

[0026]JP-A No. 2002-179707 discloses a method of producing a polymer fine
particle in which a monomer such as methyl methacrylate and the like is
thermally polymerized in supercritical carbon dioxide using a radical
polymerization initiator which is a polymer having a specific structure
substantially soluble in supercritical carbon dioxide.

[0027]JP-A No. 2002-128808 discloses a method of producing a polymer in
which a polymerizable monomer such as methyl methacrylate, styrene and
the like is thermally radical-polymerized in supercritical carbon dioxide
in the presence of a specific non-polymerizable dispersing agent such as
docosanoic acid, myristic acid and the like.

[0029]As described above, though polymer production methods of thermally
polymerizing a monomer in a supercritical fluid such as supercritical
carbon dioxide and the like have been previously investigated, there is
known no method for producing a polymer in which a monomer is
photo-polymerized in a supercritical fluid.

DISCLOSURE OF THE INVENTION

[0030]The present invention has an object of providing a polymer having
juts of large height, which height is larger as compared with diameter.
Further, the present invention has an object of providing a polymer
having juts, containing an additive component for adding polymer
functions. Still further, the present invention has an object of
providing a method capable of simply producing such a polymer having
juts.

[0031]The present invention is a process for producing a polymer, which
comprises a step of carrying out photopolymerization of at least one
photopolymerizable polymerization precursor containing a photocurable
compound having two or more unsaturated bonds by irradiation with active
energy ray in a supercritical fluid or sub-critical fluid to produce a
polymer having juts.

[0032]Further, the present invention is a process for producing a polymer,
which comprises a step of carrying out photopolymerization of at least
one photopolymerizable polymerization precursor containing a photocurable
compound having two or more unsaturated bonds by irradiation with active
energy ray in a supercritical fluid or subcritical fluid in the presence
of at least one additive component for adding a polymer function to
produce a polymer having juts containing the additive component.

[0033]Further, the present invention is a polymer having juts wherein the
height of juts is 0.1-fold or more of the diameter of the juts and the
height of juts is 10 nm or more.

[0034]Further, the present invention is a polymer having juts, which
contains at least one additive component for adding a polymer function.

[0035]Here, "polymer having juts" means a polymer in the form of
projection or a polymer having one or more projections. In the case of a
polymer in the form of projection, the polymer itself is called "jut",
and in the case of a polymer having one or more projections, the
projection is called "jut". "polymer having juts" includes also, but not
limited to, a what is called polymer brush. For example, films or plates
made of a polymer and having a plurality of projections on its surface,
and projections themselves made of a polymer, are also included in the
present invention.

[0036]When the diameters of juts (lengths of juts along a direction
parallel to the surface of a base material) are not constant, the longest
diameter at the bottom of juts (longer diameter or longer edge) is called
diameter.

[0037]According to the method of the present invention, a polymer having
juts of large length, which length is larger as compared with diameter,
can be produced simply. In the resulting polymer having juts, for
example, the height of the jut is 0.1-fold or more, further, 1-fold or
more of diameter, and the height of a jut is 10 nm or more, further 1
μm or more. A polymer thus having juts of large length, which length
is larger as compared with diameter, is not obtained conventional. When
the method of the present invention is carried out in the present of at
least one additive component for adding a polymer function, a polymer
having juts containing the additive component can be produced easily.

[0038]In the present invention, the photopolymerizable polymerization
precursor to be polymerized (hereinafter, referred to also as
"polymerization precursor") and the additive component to be used
according to necessity can be appropriately selected. By changing
pressure and/or temperature in a polymerization reaction, the solubility
of the polymerization initiator and the additive component in a solvent
(supercritical fluid or subcritical fluid) can be changed, therefore, by
controlling the polymerization pressure and polymerization temperature,
the composition of the resulting polymer having juts can be controlled.
Thus, according to the production method of the present invention, a
polymer having juts having various physical properties and functions can
be obtained.

[0039]Further, by changing the composition of the polymerization precursor
to be polymerized and the additive component to be contained during
polymerization, or by varying at least one of pressure and temperature
during polymerization, and the like, it is possible to change the
composition of the resulting polymer having juts along membrane thickness
direction (direction vertical to the surface of a base material).

[0040]The polymer having juts of the present invention is expected to be
applied to various uses typically including a conventional use of a
polymer brush owing to its peculiar shape, and also expected to realize a
novel functional structure.

[0041]For example, a polymer of the present invention in which the height
of a jut is 0.1-fold or more of the diameter of a jut and the height of a
jut is 10 nm or more shows high water-repellency irrespective of the
composition of the polymer. Therefore, the polymer can impart
water-repellency equivalent to that of a fluorine-based resin such as
PTFE (polytetrafluoroethylene) and the like frequently used in water
repellent finishing treatment.

[0042]Further, according to the method of the present invention, a polymer
having juts can be formed on an active energy ray-permeable base material
disposed so as to be exposed to a supercritical fluid or subcritical
fluid. In particular, a polymerization precursor can be photo-polymerized
by irradiation with active energy ray while permeating through an active
energy ray-permeable base material so disposed that an incident surface
of active energy ray is not exposed to a supercritical fluid or
subcritical fluid and an exiting surface of active energy ray is exposed
to a supercritical fluid or subcritical fluid, to form a polymer having
juts on an active energy ray exiting surface of the active energy
ray-permeable base material. Further, the base material can be irradiated
with active energy ray via a mask pattern, to simply form a polymer
having juts selectively on a part through which active energy ray has
permeated. That is, a polymer having juts containing an additive
component having a given fine pattern can be formed on the base material.

[0043]Furthermore, by calcining a polymer having juts of the present
invention in which the additive component is at least one organometal
complex, a membrane containing as a main component a metal and/or metal
oxide having a specific fine structure (hereinafter, referred to also as
"metal membrane") can also be formed simply in which the shape of the
polymer having juts before calcination is approximately maintained.

[0044]Still further, by reducing a polymer having juts of the present
invention in which the additive component is at least one organometal
complex, the organometal complex can be converted into a metal, or
depending on the kind of a metal, into a metal oxide, to simply form a
polymer having juts containing a metal and/or metal oxide.

BRIEF DESCRIPTION OF THE DRAWINGS

[0045]FIG. 1 is a schematic constitutional view of one example of a
production apparatus used for carrying out the production method of the
present invention.

[0046]FIG. 2 is a schematic constitutional view of one example of a
production apparatus used for carrying out the production method of the
present invention.

[0047]An upper photograph of FIG. 3 is a SEM photograph of the polymer
having juts obtained in Example 1, and a lower photograph of FIG. 3 is a
XMA Pt image of the polymer having juts obtained in Example 1.

[0048]FIG. 4 is a SEM photograph of the metal Pt membrane obtained in
Example 1.

[0049]FIG. 5 is a SEM photograph of the polymer having juts obtained in
Example 5.

[0050]FIG. 6 is a SEM photograph of the polymer having juts obtained in
Example 6.

[0051]FIG. 7 is a SEM photograph of the polymer having juts obtained in
Example 7.

[0052]FIG. 8 is a SEM photograph of the polymer membrane obtained in
Reference Example 1.

[0053]FIG. 9 is a schematic sectional view of the polymer membrane
obtained in Reference Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

[0054]In the method of the present invention, a supercritical fluid or
subcritical fluid is used as a polymerization solvent.

[0055]The supercritical fluid means a fluid under condition of both
temperature and pressure over critical points, namely, under condition of
over critical temperature and over critical pressure. The critical
temperature and the critical pressure are values inherent in a substance.
For example, carbon dioxide has a critical temperature of 30.9° C.
and a critical pressure of 7.38 MPa. Methanol has a critical temperature
of 239.4° C. and a critical pressure of 8.09 MPa. Water has a
critical temperature of 374.1° C. and a critical pressure of 22.12
MPa. The subcritical fluid means a fluid manifesting the same action and
effect as of the supercritical fluid, and having a temperature in Kelvin
unit 0.65-fold or more of the critical temperature and a pressure
0.65-fold or more of the critical pressure.

[0056]The supercritical fluid or subcritical fluid can be appropriately
selected depending on the solubility of a polymerization precursor, and
the like. Examples of the supercritical fluid or subcritical fluid
include carbon dioxide, water, methane, ethane, ethylene, propane,
propylene, alcohols such as methanol and the like, ammonia, fron, carbon
monoxide and the like. Further mentioned are inorganic gases such as
nitrogen, helium, argon and the like. These supercritical fluids or
subcritical fluids can also be used in admixture of two or more. Of them,
supercritical carbon dioxide or subcritical carbon dioxide is preferable
since supercritical condition or subcritical condition is obtained at
relatively lower temperatures and lower pressures.

[0057]The use amount of the supercritical fluid or subcritical fluid can
be appropriately determined depending on a polymerization precursor and
reaction conditions and the like. For example, the charging concentration
of a polymerization precursor can be about 1 wt % to 70 wt %.

[0058]In the present invention, a supercritical fluid or subcritical fluid
is used as a reaction field, and other liquid or gas may be present.

[0059]In the present invention, a co-solvent (entrainer) helping
dissolution of a solute polymerization precursor, additive component or
photopolymerization initiator may be used for the purpose of enhancing
the concentration of a polymerization precursor, or optional components,
namely, an additive component and photopolymerization initiator in a
supercritical fluid phase or subcritical fluid phase.

[0060]The entrainer can be appropriately selected depending on the
supercritical fluid or subcritical fluid and the polymerization precursor
and the like to be used. When supercritical carbon dioxide or subcritical
carbon dioxide is used, examples of the entrainer include methanol,
ethanol, propane, butane, hexane, octane, acetic acid, ethyl acetate,
acetone, water, acetonitrile, dichloromethane and the like. The entrainer
may be used singly or in combination. The use amount of the entrainer can
be appropriately determined.

[0061]Pressure in the polymerization reaction (polymerization pressure)
can be appropriately determined depending on the properties of a
polymerization solvent, namely, a supercritical fluid or subcritical
fluid and a polymerization precursor, intended polymer and the like. The
polymerization pressure is preferably 0.65-fold or more of the critical
pressure of a fluid, and more preferably the critical pressure or more.
When supercritical carbon dioxide or subcritical carbon dioxide is used,
the polymerization pressure is preferably 5 MPa or more, more preferably
7 MPa or more, and particularly preferably not lower than 7.4 MPa which
is a critical pressure. When the polymerization pressure is within this
range, the polymerization reaction progresses more successfully, and a
polymer of higher quality is obtained. The upper limit of the
polymerization pressure is not particularly restricted, and from the
standpoint of the pressure-resistance of an apparatus and the like, it
can be usually set in a range of 150 MPa or lower. The polymerization
pressure may be kept constant from initiation until completion of
polymerization, alternatively, the pressure may be subjected to variation
during polymerization, such as increase in pressure or decrease in
pressure with progress of polymerization.

[0062]Temperature in the polymerization reaction (polymerization
temperature) can be appropriately determined depending on the properties
of a polymerization solvent, namely, a supercritical fluid or subcritical
fluid and a polymerization precursor, intended polymer and the like. The
polymerization temperature is preferably 0.65-fold or more of the
critical temperature of a fluid, and more preferably the critical
pressure or more. When supercritical carbon dioxide or subcritical carbon
dioxide is used, the polymerization temperature is preferably 20°
C. or more, more preferably 30° C. or more, and particularly
preferably not lower than 31° C. which is a critical temperature.
When the polymerization temperature is within this range, the
polymerization reaction progresses more successfully, and a polymer of
higher quality is obtained. Though the upper limit of the polymerization
temperature is not particularly restricted, it can be usually set in a
range of 250° C. or lower. The polymerization temperature may be
kept constant from initiation until completion of polymerization,
alternatively, the temperature may be subjected to variation during
polymerization.

[0063]Specifically, it is preferable to photopolymerize a polymerization
precursor in carbon dioxide having a pressure of 5 MPa or more and a
temperature of 20° C. or more, further, it is preferable to
photopolymerize a polymerization precursor in carbon dioxide having a
pressure of 7 MPa or more and a temperature of 30° C. or more.

[0064]The supercritical fluid or subcritical fluid can have density and
polarity changed by pressure and temperature. By this, the solubility of
a polymerization precursor and an optional component, additive component,
in a solvent (supercritical fluid or subcritical fluid) can be changed.
Therefore, for example, in the case of use of an additive component and
in the case of use of two or more polymerization precursors, the
composition of the resulting polymer can be controlled by controlling
polymerization pressure and polymerization temperature. By varying at
least one of pressure and temperature during polymerization, it is also
possible to change the composition of the resulting polymer, for example,
along a direction vertical to the surface of a base material.

[0065]In the method of the present invention, photopolymerization is
carried out by irradiation with active energy ray in the presence of at
least one polymerization precursor (monomer or the like), and if
necessary, at least one additive component and a photopolymerization
initiator, in the supercritical fluid or subcritical fluid as described
above. Here, when only a polymerization precursor having one unsaturated
bond is polymerized, a network structure is not formed and hardening does
not occurs. For hardening, a polymerization precursor having two or more
unsaturated bonds is necessary. Therefore, in the present invention, the
polymerization precursor to be polymerized is allowed to contain at least
one photopolymerizable compound which is a compound having two or more
unsaturated bonds.

[0066]active energy ray used for irradiation can be appropriately
determined depending on the polymerization precursor, photopolymerization
initiator and the like. The active energy ray includes ultraviolet ray
having wavelengths from 10 to 380 nm, visible ray having wavelengths from
380 to 780 nm, near infrared ray having wavelengths from 780 nm (0.78
μm) to 2.5 μm, and the like. In may cases, ultraviolet ray or
visible ray having wavelengths of 500 nm or less, further, ultraviolet
ray or visible ray having wavelengths of 420 nm or less, are used, and
particularly, ultraviolet ray having wavelengths of 380 nm or less,
further, ultraviolet ray having wavelengths of 330 nm or less, are used,
as the active energy ray.

[0067]The active energy ray may not be a radiation having single
wavelength or having one peak in its spectral distribution (emission
distribution), and the active energy ray may have any spectral
distribution providing light of the above-mentioned wavelength is
contained.

[0069]The dose (accumulated light quantity) of active energy ray can be
appropriately determined depending on the degree of polymerization of a
given polymer, the height of a jut of a polymer having juts, and the
like. The dose of active energy ray can be, for example, 0.5 mJ/cm2
to 100 J/cm2, and preferably, 1 mJ/cm2 or more and 10
J/cm2 or less.

[0071]The dose of active energy ray can be controlled by irradiation time,
lamp output and the like.

[0072]The intensity of active energy ray can be appropriately determined,
and for example, can be 0.01 mW/cm2 to 1 tera W/cm2
(TW/cm2). The irradiation time of active energy ray may be
advantageously determined so as to obtain given irradiation amount
according to its intensity.

[0073]In the present invention, a polymerization precursor and if
necessary, an additive component and nano particles (ultrafine particles
having an average particle size of, for example, 100 nm or less), are
preferably dissolved and dispersed uniformly, then, irradiated with
active energy ray to effect photopolymerization. Examples of the nano
particles include nano carbon, CdSe and the like. By this, a polymer
having juts in which an additive component and nano particles are
uniformly dispersed can be produced. If necessary, other additives can
also be compounded.

[0074]The polymerization precursor is not particularly restricted
providing it is dissolved in a solvent supercritical fluid or subcritical
fluid and it has photopolymerizability. The polymerization precursor can
also be polymerized under condition of partial dissolution thereof in a
supercritical fluid or subcritical fluid. The polymerization precursor
may be a monomer, oligomer or polymer. As described above, in the present
invention, a photopolymerizable compound which is a compound having two
or more unsaturated bonds is used as the polymerization precursor. As the
polymerization precursor, a polymerization precursor having one
unsaturated bond can also be used together with a photopolymerizable
compound.

[0075]Examples of the polymerization precursor include compounds having at
least one group selected from the group consisting of a maleimide group
optionally having a substituent, (meth)acryloyl group optionally having a
substituent, cyclic ether structure optionally having a substituent,
alkenyl group optionally having a substituent, vinylene group optionally
having a substituent, and styryl group and azide group optionally having
a substituent. Here, the (meth)acryloyl group means an acryloyl group and
a methacryloyl group. When two or more of these groups are contained,
only the same group may be contained, or different groups may be
contained. The substituent is not particularly restricted providing it
does not inhibit a polymerization reaction, and examples thereof include
hydrocarbon groups having 12 or less carbon atoms, halogen atoms, amino
groups, carboxyl group, hydroxyl group, cyano group and the like.

[0076]Preferable as the polymerization precursor are self-luminous
polymerizable compounds which are compounds photopolymerizing in the
absence of a photopolymerization initiator.

[0077]As the polymerization precursor which is a self luminous
polymerizable compound, for example, maleimide-based compounds having at
least two maleimide groups are preferable. Specifically mentioned are
maleimide-based compounds of the following general formula (1).

##STR00001##

(wherein, A represents a hydrocarbon group optionally having a
substituent, or a (poly)ether connecting chain or (poly)ether residue,
(poly)ester connecting chain or (poly)ester residue, (poly)urethane
connecting chain or (poly)urethane residue or (poly)carbonate connecting
chain or (poly)carbonate residue having a molecular weight of 40 to
100000 obtained by connecting hydrocarbon groups optionally having a
substituent via at least one bond selected from the group consisting of
an ether bond, ester bond, urethane bond and carbonate bond. B represents
an ether bond, ester bond, urethane bond or carbonate bond. R represents
a hydrocarbon group optionally having a substituent. m represents an
integer of 2 to 6. It is not necessary that Bs and Rs are all the same,
and two or more different groups may be present in admixture.)

[0078]In the general formula (I), m is preferably an integer of 2 to 6
from the standpoint of formation of a hardened membrane from a single
maleimide-based compound.

[0079]In the general formula (I), R is preferably an alkylene group,
cycloalkylene group, arylalkylene group or cycloalkylalkylene group.
Here, the alkylene group may be straight or branched. The arylalkylene
group or cycloalkylalkylene group may have an aryl group or cycloalkyl
group in the main chain, and may have an aryl group or cycloalkyl group
in a branched chain. R is preferably a straight chain alkylene group
having 1 to 5 carbon atoms or a branched alkylene group having 1 to 5
carbon atoms from the stand point of curability.

[0080]Specific examples of R in the general formula (1) include straight
chain alkylene groups such as a methylene group, ethylene group,
trimethylene group, tetramethylene group, pentamethylene group,
hexamethylene group, heptamethylene group, octamethylene group,
nonamethylene group, decamethylene group, undecamethylene group,
dodecamethylene group and the like; branched alkylene groups such as a
1-methylethylene group, 1-methyl-trimethylene group,
2-methyl-trimethylene group, 1-methyl-tetramethylene group,
2-methyl-tetramethylene group, 1-methyl-pentamethylene group,
2-methyl-pentamethylene group, 3-methyl-pentamethylene group,
neopentylene group and the like; cycloalkylene groups such as a
cyclopentylene group, cyclohexylene group and the like; arylalkylene
groups having an aryl group in the main chain or side chain such as a
benzylene group, 2,2-diphenyl-trimethylene group, 1-phenyl-ethylene
group, 1-phenyl-tetraethylene group, 2-phenyl-tetraethylene group and the
like; cycloalkyl-alkylene groups having a cycloalkyl group in the main
chain or side chain such as a cyclohexylmethylene group,
1-cyclohexyl-ethylene group, 1-cyclohexyl-tetraethylene group,
2-cyclohexyl-tetraethylene group and the like.

[0081]In the general formula (1), A represents a hydrocarbon group
optionally having a substituent, or a (poly)ether connecting chain or
(poly)ether residue (A-1), (poly)ester connecting chain or (poly)ester
residue (A-2), (poly)urethane connecting chain or (poly)urethane residue
(A-3) or (poly)carbonate connecting chain or (poly)carbonate residue
(A-4) having a molecular weight of 40 to 100000 obtained by connecting
hydrocarbon groups optionally having a substituent via at least one bond
selected from the group consisting of an ether bond, ester bond, urethane
bond and carbonate bond. A may also be connecting chain constituted of an
oligomer or polymer containing repetition of these connecting chains as
one unit of repetition.

[0082]When A in the general formula (1) is a hydrocarbon group optionally
having a substituent, specific examples thereof include those hydrocarbon
groups mentioned as specific examples of R.

[0083]Further, A in the general formula (1) includes;

[0084](A-1) connecting chains or residues constituted of a (poly)ether
(poly)ol having a molecular weight of 40 to 100000 having one unit or
repeating units in which at least one hydrocarbon group selected from the
group consisting of straight chain alkylene groups, branched alkylene
groups, cycloalkylene groups and aryl groups is bonded by an ether bond;

[0085](A-2-1) connecting chains or residues constituted of a (poly)ether
(poly)ol having a molecular weight of 40 to 100000 having one unit or
repeating units in which at least one hydrocarbon group selected from the
group consisting of straight chain alkylene groups, branched alkylene
groups, cycloalkylene groups and aryl groups is bonded by an ester bond;

[0086](A-2-2) connecting chains or residues constituted of a
(poly)carboxylic acid {(poly)ether (poly)ol}ester carrying a
polycarboxylic acid residue at the end obtained by esterification of a
di-, tri-, penta-, hexa-carboxylic acid (hereinafter, abbreviated as
polycarboxylic acid) with a (poly)ether (poly)ol having a molecular
weight of 40 to 100000 having one unit or repeating units in which at
least one hydrocarbon group selected from the group consisting of
straight chain alkylene groups, branched alkylene groups, cycloalkylene
groups and aryl groups is bonded by an ether bond;

[0087](A-2-3) connecting chains or residues constituted of a
(poly)carboxylic acid {(poly)ester (poly)ol}ester carrying a
polycarboxylic acid residue at the end obtained by esterification of a
polycarboxylic acid with a (poly)ester (poly)ol having a molecular weight
of 40 to 100000 having one unit or repeating units in which at least one
hydrocarbon group selected from the group consisting of straight chain
alkylene groups, branched alkylene groups, cycloalkylene groups and aryl
groups is bonded by an ether bond and an ester bond;

[0088](A-5) connecting chains or residues obtained by ring-opening of a
(poly)epoxide having a molecular weight of 100 to 40000 having one unit
or repeating units in which at least one hydrocarbon group selected from
the group consisting of straight chain alkylene groups, branched alkylene
groups, cycloalkylene groups and aryl groups is bonded by an ether bond;

[0089](A-3-1) connecting chains or residues constituted of a (poly)ether
(poly)isocyanate obtained by urethanization of an organic
(poly)isocyanate with a (poly)ether (poly)ol having a molecular weight of
40 to 100000 having one unit or repeating units in which at least one
hydrocarbon group selected from the group consisting of straight chain
alkylene groups, branched alkylene groups, cycloalkylene groups and aryl
groups is bonded by an ether bond;

[0090](A-3-2) connecting chains or residues constituted of a (poly)ester
(poly)isocyanate obtained by urethanization of an organic
(poly)isocyanate with a (poly)ester (poly)ol having a molecular weight of
40 to 100000 having one unit or repeating units in which at least one
hydrocarbon group selected from the group consisting of straight chain
alkylene groups, branched alkylene groups, cycloalkylene groups and aryl
groups is bonded by an ester bond;

[0091](A-4) connecting chains or residues constituted of a carbonate of a
(poly)ether (poly)ol having a molecular weight of 40 to 100000 having one
unit or repeating units in which at least one hydrocarbon group selected
from the group consisting of straight chain alkylene groups, branched
alkylene groups, cycloalkylene groups and aryl groups is bonded by an
ether bond; and the like.

[0092](A-2-1), (A-2-2) and (A-2-3) are used as the (poly)ester connecting
chain or (poly)ester residue (A-2) in the general formula (1). (A-3-1)
and (A-3-2) are used as the (poly)urethane connecting chain of
(poly)urethane residue (A-3) in the general formula (1).

[0094]Examples of the (poly)ester (poly)ol constituting the
above-mentioned connecting chain or residue (A-2-1) include polyalkylene
glycols such as polyethylene glycol, polypropylene glycol, polybutylene
glycol, polytetramethylene glycol and the like, e-caprolactone modified
substances, γ-butyrolactone modified substances, d-valerolactone
modified substances or methylvalerolactone modified substances of
alkylene glycols such as ethylene glycol, propanediol, propylene glycol,
tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl
glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin,
ditrimethylolpropane, dipentaerythritol and the like; aliphatic polyester
polyols as an esterified substance of an aliphatic dicarboxylic acid such
as adipic acid, dimmer acid and the like with a polyol such as neopentyl
glycol, methylpentanediol and the like; polyester polyols such as
aromatic polyester polyols as an esterified substance of an aromatic
dicarboxylic acid such as terephthalic acid with a polyol such as
neopentyl glycol and the like; esterified substances of a poly-valent
hydroxyl group compound such as polycarbonate polyol, acryl polyol,
polytetramethylenehexaglyceryl ether (tetrahydrofuran modified substance
of hexaglycerin) and the like with a dicarboxylic acid such as fumaric
acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid,
sebacic acid, maleic acid and the like; poly-valent hydroxyl
group-containing compounds such as monoglycerides obtained by a
transesterification reaction of a poly-valent hydroxyl group-containing
compound such as glycerin and the like with a fatty ester, and the like.

[0098]Examples of the (poly)ether (poly)isocyanate constituting the
above-mentioned connecting chain or residue (A-3) include aliphatic
diisocyanate compounds such as methylene diisocyanate, hexamethylene
diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene
diisocyanate, lysine diisocyanate, dimer acid diisocyanate and the like;
aromatic diisocyanate compounds such as 2,4-tolyene diisocyanate, dimmer
of 2,4-tolyene diisocyanate, 2,6-tolyene diisocyanate, p-xylene
diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate and
the like; (poly)ether (poly)isocyanates obtained by a urethanization
reaction of a polyisocyanate such as alicyclic diisocyanates such as
isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate),
methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate,
1,3-(isocyanatemethylene)cyclohexane and the like with a (poly)ether
(poly)ol, and the like.

[0099]Examples of the (poly)ether (poly)ol used in the reaction with a
polyisocyanate include polyalkylene glycols such as polyethylene glycol,
polypropylene glycol, polybutylene glycol, polytetramethylene glycol and
the like; ethylene oxide modified substances, propylene oxide modified
substances, butylene oxide modified sub-stances or tetrahydrofuran
modified substances of alkylene glycols such as ethylene glycol,
propanediol, propylene glycol, tetramethylene glycol, pentamethylene
glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane,
pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol and
the like. Of them, various modified substances of alkylene glycols are
preferable. Further, as the (poly)ether (poly)ol used in the reaction
with a polyisocyanate, mentioned are copolymers of ethylene oxide and
propylene oxide, copolymers of propylene oxide with tetrahydrofuran,
copolymers of ethylene glycol with tetrahydrofuran; hydrocarbon-based
polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol,
polybutadiene glycol, hydrogenated polybutadiene glycol and the like;
poly-valent hydroxyl group compounds such as polytetramethylene
hexaglyceryl ether (tetrahydrofuran modified substances of hexaglycerin)
and the like.

[0100]Examples of the (poly)ester (poly)isocyanate constituting the
above-mentioned connecting chain or residue (A-3-1) include (poly)ester
(poly)isocyanates obtained by urethanization of a polyisocyanate
mentioned for the connecting chain or residue (A-1) with a (poly)ester
(poly)ol.

[0101]Examples of the (poly)ester (poly)ol used in the reaction with a
polyisocyanate include ε-caprolactone modified substances,
γ-butyrolactone modified substances, d-valerolactone modified
substances or methylvalerolactone modified substances of alkylene glycols
such as ethylene glycol, propanediol, propylene glycol, tetramethylene
glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,
trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane,
dipentaerythritol and the like; aliphatic polyester polyols as an
esterified substance of an aliphatic dicarboxylic acid such as adipic
acid, dimmer acid and the like with a polyol such as neopentyl glycol,
methylpentanediol and the like; polyester polyols such as aromatic
polyester polyols as an esterified substance of an aromatic dicarboxylic
acid such as terephthalic acid with a polyol such as neopentyl glycol and
the like; esterified substances of a poly-valent hydroxyl group compound
such as polycarbonate polyol, acryl polyol,
polytetramethylenehexaglyceryl ether (tetrahydrofuran modified substance
of hexaglycerin) and the like with a dicarboxylic acid such as fumaric
acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid,
sebacic acid, maleic acid and the like; poly-valent hydroxyl
group-containing compounds such as monoglycerides obtained by a
transesterification reaction of a poly-valent hydroxyl group-containing
compound such as glycerin and the like with a fatty ester, and the like.

[0102]Examples of the (poly)ether (poly)ol constituting the
above-mentioned connecting chain or residue (A-4) include (poly)ether
(poly)ols mentioned for the connecting chain or residue (A-1).

[0103]The compound used for carbonation with a (poly)ether (poly)ol
includes diethyl carbonate, dipropyl carbonate, phosgene and the like.
Polycarbonation can be performed also by alternate polymerization of an
epoxide with carbon dioxide.

[0104]Of them, preferable as A in the general formula (1) are (poly)ether
connecting chains or (poly)ether residues (A-1) or (poly)ester connecting
chains or (poly)ester residues (A-2) having a molecular weight of 100 to
100000 obtained by connecting at least one group selected from the group
consisting of straight chain alkylene groups having 2 to 24 carbon atoms,
branched alkylene groups having 2 to 24 carbon atoms, alkylene groups
having 2 to 24 carbon atoms carrying a hydroxyl group, cycloalkylene
groups, aryl groups and arylalkylene groups via at least one bond
selected from the group consisting of an ether bond and an ester bond,
and more preferable are (poly)ether connecting chains or (poly)ether
residues (A-1) having a molecular weight of 100 to 100000 having a
repeating unit containing a straight chain alkylene group having 2 to 24
carbon atoms, branched alkylene group having 2 to 24 carbon atoms,
alkylene group having 2 to 24 carbon atoms carrying a hydroxyl group
and/or aryl group or (poly)ester connecting chains or (poly)ester
residues (A-2) having a molecular weight of 100 to 100000 having a
repeating unit containing a straight chain alkylene group having 2 to 24
carbon atoms, branched alkylene group having 2 to 24 carbon atoms,
alkylene group having 2 to 24 carbon atoms carrying a hydroxyl group
and/or aryl group.

[0105]As the maleimide-based compound represented by the general formula
(1), preferable are maleimide-based compounds in which R is an alkylene
group having 1 to 5 carbon atoms, B is an ester bond represented by
--COO-- or --OCO--, and A is a (poly)ether connecting chain or
(poly)ether residue (A-1) having a molecular weight of 100 to 1000 having
a repeating unit containing a straight chain alkylene group having 2 to 6
carbon atoms, branched alkylene group having 2 to 6 carbon atoms or
alkylene group having 2 to 6 carbon atoms carrying a hydroxyl group, from
the standpoint of curability.

[0106]As such maleimide-based compounds, for example, polyether
bismaleimide acetates of the following general formula (2) are mentioned.

##STR00002##

(wherein, R1 represents an alkylene group and n represents an integer
of 1 to 1000).

[0107]The maleimide-based compound of the general formula (1) can be
synthesized, for example, by known methods from a maleimide-based
compound having a carboxyl group and a compound reacting with a carboxyl
group. Examples of the compound reacting with a carboxyl group include 2
to 6-functional polyols or polyepoxides having an average molecular
weight of 100 to 1000000 having one unit or repeating units in which at
least one hydrocarbon group selected from the group consisting of
straight chain alkylene groups, branched alkylene groups, cycloalkylene
groups and aryl groups is bonded by an ether bond and/or ester bond.

[0108]The maleimide-based compound of the general formula (1) can be
synthesized by known methods from a maleimide-based compound having a
carboxyl group and a compound reacting with a carboxyl group. Examples of
the compound reacting with a carboxyl group include di-, tri-, penta-,
hexa-carboxylic acids, (poly)isocyanates, carbonates or phosgenes having
2 to 6 carboxyl groups, ether bonds or ester bonds in one molecule having
an average molecular weight of 100 to 1000000 having one unit or
repeating units in which at least one hydrocarbon group selected from the
group consisting of straight chain alkylene groups, branched alkylene
groups, cycloalkylene groups and aryl groups is bonded by an ether bond
and/or ester bond.

[0109]The polymerization precursor includes, in addition, compounds as
described below.

[0112]Further, maleimide-based compounds obtained by a reaction of
3,4,4'-triaminodiphenylmethane, triaminophenol and the like with maleic
anhydride, and maleimide-based compounds obtained by a reaction of
tris-(4-aminophenyl)-phosphate or tris-(4-aminophenyl)-thiophosphate with
maleic anhydride, are also mentioned.

[0114]As the maleimide-based compound, oligomers and polymers having at
least one maleimide group are also mentioned.

[0115]The kind of this oligomer is not particularly restricted, and for
example, those obtained by a Michael addition reaction of the
above-mentioned maleimide-based compound and polyamines, and those
obtained by a reaction of maleic acids and/or maleic anhydrides and a
diamine, and the like are mentioned. Further, those obtained by a
reaction of a polyimide precursor having an end anhydride group obtained
by reacting tetracarboxylic dianhydride and diamine with a hydroxyl
group-containing maleimide compound such as a maleimide compound as a
reaction product of an epoxy resin and maleimide group-containing
monocarboxylic acid, and those obtained by a reaction of a polyimide
precursor having an end anhydride group obtained by reacting
tetracarboxylic dianhydride and diamine, with a hydroxyl group-containing
maleimide compound such as a maleimide compound as a reaction product of
an epoxy resin and maleimide group-containing monocarboxylic acid, and
with a polyol compound, and the like are mentioned.

[0116]Furthermore, also mentioned are compounds in which at least one
maleimide group is bonded to polymer components or oligomer components
such as a urethane-based resin, epoxy-based resin, polyester-based resin,
polyether-based resin, alkyd-based resin, polyvinyl chloride-based resin,
fluorine-based resin, silicone-based resin, vinyl acetate-based resin,
phenol-based resin, polyamide resin and resins obtained by modifying two
or more of these resins, and the like.

[0124]Also mentioned are (meth)acryloyl group-containing silicone
oligomers in which at least one (meth)acryloyl group or group containing
a (meth)acryloyl group is bonded to at least one of end silicon atoms.
Regarding the structure of a silicon oligomer itself, for example,
mentioned are those containing at least one of an alkylsiloxane structure
unit having 2 or more carbon atoms, arylsiloxane structure unit or
aralkylsiloxane structure unit.

[0125]Furthermore, also mentioned are compounds in which at least one
(meth)acryloyl group is bonded to polymer components or oligomer
components such as a urethane-based resin, epoxy-based resin,
polyester-based resin, polyether-based resin, alkyd-based resin,
polyvinyl chloride-based resin, fluorine-based resin, silicone-based
resin, vinyl acetate-based resin, phenol-based resin, polyamide resin and
resins obtained by modifying two or more of these resins, and the like.

[0126]As the compound having at least one cyclic ether structure,
mentioned are ring-containing ether compounds having at least one cyclic
ether structure containing 2 to 12 carbon atoms and 1 to 6 oxygen atoms,
particularly, a cross-linked structure containing --O--. More
specifically, compounds having an epoxy ring such as a glycidyl group and
the like are mentioned.

[0127]Examples of the compound having at least one cyclic ether structure
include ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl
ether and the like.

[0128]Also mentioned are oligomers and polymers having at least one cyclic
ether structure.

[0129]Examples of the oligomer having a cyclic ether structure include
oligoethylene glycol diglycidyl ether and the like.

[0130]Further, also mentioned are compounds in which at least one group
having such a cyclic ether structure is bonded to polymer components or
oligomer components such as a urethane-based resin, epoxy-based resin,
polyester-based resin, polyether-based resin, alkyd-based resin,
polyvinyl chloride-based resin, fluorine-based resin, silicone-based
resin, vinyl acetate-based resin, phenol-based resin, polyamide resin and
resins obtained by modifying two or more of these resins, and the like.

[0131]The compound having at least one alkenyl group includes compounds
having at least one vinyl group and/or allyl group. Examples of the
compound having at least one alkenyl group include polyvinylcinnamates
and the like.

[0132]Further, also mentioned are compounds in which at least one alkenyl
group is bonded to polymer components or oligomer components such as a
urethane-based resin, epoxy-based resin, polyester-based resin,
polyether-based resin, alkyd-based resin, polyvinyl chloride-based resin,
fluorine-based resin, silicone-based resin, vinyl acetate-based resin,
phenol-based resin, polyamide resin and resins obtained by modifying two
or more of these resins, and the like.

[0133]Examples of the compound having at least one vinylene group include
compounds having an ethylenically unsaturated bond, unsaturated
polyesters and the like. As the compound having at least one vinylene
group, compounds having at least one cinnamyl group
(C6H5--CH═CH--CH2--) or cinnamylidene group
(C6H5--CH═CH--CH═) are also mentioned. As such a
compound, for example, polyvinyl cinnamate is mentioned. Polyvinyl
cinnamate can be obtained, for example, by reacting polyvinyl alcohol
with C6H5--CH═CH--CH2--COCl.

[0134]Further, also mentioned are compounds in which at least one vinylene
group is bonded to polymer components or oligomer components such as a
urethane-based resin, epoxy-based resin, polyester-based resin,
polyether-based resin, alkyd-based resin, polyvinyl chloride-based resin,
fluorine-based resin, silicone-based resin, vinyl acetate-based resin,
phenol-based resin, polyamide resin and resins obtained by modifying two
or more of these resins, and the like.

[0135]Examples of the compound having at least one styryl group include
styrene, a-methylstyrene, p-methylstyrene, a-methyl-p-methylstyrene,
p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, chlorostyrene,
bromostyrene and the like. Also mentioned are
polyvinylbenzalacetophenones, polyvinylstyrylpyridines and the like.

[0136]Further, also mentioned are compounds in which at least one styryl
group is bonded to polymer components or oligomer components such as a
urethane-based resin, epoxy-based resin, polyester-based resin,
polyether-based resin, alkyd-based resin, polyvinyl chloride-based resin,
fluorine-based resin, silicone-based resin, vinyl acetate-based resin,
phenol-based resin, polyamide resin and resins obtained by modifying two
or more of these resins, and the like.

[0137]Examples of the compound having at least one azide group include
2,6-bis(4-azidebenzylidene)chclohexanone,
2,6-bis(4'-azidebenzyl)methylcyclohexanone and the like.

[0138]Further, also mentioned are compounds in which at least one azide
group is bonded to polymer components or oligomer components such as a
urethane-based resin, epoxy-based resin, polyester-based resin,
polyether-based resin, alkyd-based resin, polyvinyl chloride-based resin,
fluorine-based resin, silicone-based resin, vinyl acetate-based resin,
phenol-based resin, polyamide resin and resins obtained by modifying two
or more of these resins, and the like.

[0139]The monomer copolymerizable with the monomers as described above
includes cyano group-containing vinyl compounds such as acrylonitrile and
methacrylonitrile and the like; halogen-containing vinyl compounds such
as vinyl chloride and vinylidene chloride and the like; organic acid
group-containing vinyl compounds such as vinyl acetate and vinyl
propionate and the like; reactive monomers such as ethylene, maleic acid,
itaconic acid and the like; acryl-modified silicones; cross-linkable
copolymerization monomers such as chloroethyl vinyl ether, allyl glycidyl
ether, ethylidenenorbornene, divinylbenzene, triallyl cyanurate, triallyl
isocyanurate and the like.

[0140]The polymerization precursors as described above may be used singly
or in combination of two or more.

[0141]It is also possible to vary the composition of the resulting
polymer, for example, along a direction vertical to the surface of a base
material by changing, during polymerization, the composition of a
polymerization precursor to be polymerized.

[0142]In the production method of the present invention, the additive
component for adding polymer functions is not particularly restricted,
and may be an organic sub-stance or inorganic substance. The additive
component to be used can be appropriately selected depending on the
composition, physical properties and the like of a desired polymer.
Examples of the functions to be added by the additive component include,
but not limited to, adsorption function, separation function, catalytic
function, medicinal function and the like.

[0143]The additive component is preferably a component performing
photopolymerization under condition of partial dissolution thereof in a
supercritical fluid or sub-critical fluid, and may also be a component
performing photopolymerization under condition of dispersion thereof in a
supercritical fluid or subcritical fluid.

[0144]As the additive component, for example, compounds (including also
complex) containing a metal are mentioned. Examples of the compound
containing a metal include those of the following general formula (3),
those of the following general formula (4), those of the following
general formula (5), those of the following general formula (6), those of
the following general formula (7) and those of the following general
formula (8).

M1pX1q (3)

[0145](wherein, M1 represents a metal element, X1 represents O,
S, SO4 or PO4. p and q represent the ratio of M1 to
X1, and determined by the valency of a metal element M1. When
two or more X1s are present, it is not necessary that all
X1s are the same, and two or more kinds of moieties may be
present in admixture.)

M2X2t (4)

(wherein, M2 represent a metal element, and X2 represents F, Cl,
Br, I, CN, NO3, ClO4 or NR01R02R03R04
(wherein, R01, R02, R03 and R04 represent each
independently hydrogen, hydrocarbon group or CF3. R01,
R02, R03 and R04 may be the same or different. R01,
R02, R03 and R04 may also represent a poly-valent ligand
such as phthalocyanine and the like.). t represents the ratio of M2
to X2, and determined by the valency of a metal element M2.
When two or more X2s are present, it is not necessary that all
X2s are the same, and two or more kinds of moieties may be
present in admixture.)

M3(OR3)1 (5)

(wherein, M3 represents a metal element, R3 represents hydrogen,
hydrocarbon group or CF3. i represents the ratio of M3 to
(OR3), and determined by the valency of a metal element M3.
When two or more (OR3)s are present, it is not necessary that
all R3s are the same, and two or more kinds of moieties may be
present in admixture.)

M4(OCOR4)j (6)

(wherein, M4 represents a metal element, R4 represents hydrogen,
hydrocarbon group or CF3. j represents the ratio of M4 to
(OCOR4), and determined by the valency of a metal element M4.
When two or more (OCOR4)s are present, it is not necessary that
all R4s are the same, and two or more kinds of moieties may be
present in admixture.)

M5(OSO3R5)k (7)

(wherein, M5 represents a metal element, R5 represents hydrogen,
hydrocarbon group or CF3. k represents the ratio of M5 to
(OSO3R5), and determined by the valency of a metal element
M5. When two or more (OSO3R5)s are present, it is not
necessary that all R5s are the same, and two or more kinds of
moieties may be present in admixture.)

M6(R6COCH2COR7)1 (8)

(wherein, M6 represents a metal element, R6 and R7
represent each independently hydrogen, hydrocarbon group or CF3. I
represents the ratio of M6 to (R6COCH2COR7), and
determined by the valency of a metal element M6. When two or more
(R6COCH2COR7)s are present, it is not necessary that
all R6s and R7s are the same, and two or more kinds
of moieties may be present in admixture.)

[0146]p and q in the above-mentioned formula (3), t in the above-mentioned
formula (4), i in the above-mentioned formula (5), j in the
above-mentioned formula (6), k in the above-mentioned formula (7) and I
in the above-mentioned formula (8) are determined by the valency of a
metal element as described above and, for example, when M1 in the
above-mentioned formula (3) is an a-valent metal, then, (p,q)=(1,a/2),
and when M2 in the above-mentioned formula (4) is a b-valent metal,
then, t=b.

[0147]M1 in the above-mentioned formula (3), M2 in the
above-mentioned formula (4), M3 in the above-mentioned formula (5),
M4 in the above-mentioned formula (6), M5 in the
above-mentioned formula (7) and M6 in the above-mentioned formula
(8) are not particularly restricted, and preferable are, for example,
nickel (Ni), gold (Au), silver (Ag), copper (Cu), indium (In), palladium
(Pd), platinum (Pt), tin (Sn), tungsten (W), aluminum (Al) and the like.
M1 in the above-mentioned formula (3), M2 in the
above-mentioned formula (4), M3 in the above-mentioned formula (5),
M4 in the above-mentioned formula (6), M5 in the
above-mentioned formula (7) and M6 in the above-mentioned formula
(8) may be present in plural number. That is, an alloy composed of the
above-mentioned metal elements may also be used.

[0148]In the above-mentioned formula (3), the above-mentioned formula (4),
the above-mentioned formula (5), the above-mentioned formula (6), the
above-mentioned formula (7) and the above-mentioned formula (8), the
carbon number of a hydrocarbon group is not particularly restricted and
preferably from 1 to 50. Examples of these hydrocarbon groups include a
saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon
group, alicyclic hydrocarbon group, alicyclic-aliphatic hydrocarbon
group, aromatic hydrocarbon group, aromatic-aliphatic hydrocarbon group,
and the like. The aliphatic hydrocarbon group may be straight or
branched.

[0150]The content of a metal contained in the above-mentioned metal
compound, namely, p and q in the above-mentioned formula (3), t in the
above-mentioned formula (4), i in the above-mentioned formula (5), j in
the above-mentioned formula (6), k in the above-mentioned formula (7) and
I in the above-mentioned formula (8) are not particularly restricted.

[0151]More specifically, examples of the additive component include
organometal complexes such as organoplatinum, complex, organopalladium
complex and the like.

[0153]The organopalladium complex is not particularly restricted, and
examples thereof include PdCl2[P(Me)3]4,
PdCl2[PBu3]2, Pd(PPh3)4 and the like. Also
mentioned are Pd3(O2CCH3)6, Pd(acac)2 and the
like. Wherein, acac represents acetylacetonato.

[0154]The organometal complex as the additive component include,
additionally, an organoruthenium complex, organocobalt complex,
organorhodium complex, or ganoiridium complex, organonickel complex, and
the like. Also these complexes may have any ligands.

[0155]When an organometal complex is contained as the additive component,
it is also possible to calcine the produced polymer having juts to
metallize this. In this case, it is preferable to use an organometal
complex carrying a hydrocarbon ligand as the additive component.

[0156]The additive component includes also organic compounds such as
various medicinal components, for example, known blood circulation
promoters, antiphlogistics, anti-inflammatory analgesics, antioxidants,
antihistamines, antibacterial agents, antibiotics, steroids and the like.

[0158]The additive components for adding polymer functions as described
above may be used singly or in combination of two or more.

[0159]It is also possible to vary the composition of the resulting
polymer, for example, along a direction vertical to the surface of a base
material by changing, during polymerization, the composition and amount
of an additive component.

[0160]The use amount of the additive component for adding polymer
functions can be appropriately determined depending on the composition
and physical properties of a desired polymer. The use amount of the
additive component can be, for example, about 0.001 to 100 parts by
weight based on 100 parts by weight of a polymerization precursor to be
polymerized. Usually, the use amount of the additive component is
preferably 0.1 part by weight or more based on 100 parts by weight of a
polymerization precursor to be polymerized, and preferably 50 parts by
weight or less based on 100 parts by weight of a polymerization precursor
to be polymerized.

[0161]When a polymerization precursor other than self luminous
polymerizable compounds is polymerized, a photopolymerization initiator
is necessary. The photopolymerization initiator is not particularly
restricted providing it is dissolved in a supercritical fluid or a
subcritical fluid or a polymerization precursor, and can be appropriately
determined depending on the supercritical fluid or subcritical fluid or
polymerization precursor to be used.

[0165]The photopolymerization initiator as described above may be used
singly or in combination of two or more.

[0166]The use amount of the photopolymerization initiator can be, for
example, about 0.1 to 30 parts by weight based on 100 parts by weight of
a polymerization precursor.

[0167]If necessary, the above-mentioned photopolymerization initiator and
photopolymerization initiation aid (sensitizer) can be used in
combination. Examples of the photopolymerization initiation aid include
2-dimethylaminoethylbenzoate, N,N'-dimethylaminoethyl methacrylate,
isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate and the
like.

[0168]In the present invention, it is possible to use a spectral
sensitizer showing a mutual action property with a polymer to be produced
and a photopolymerization initiator. Examples of the spectral sensitizer
include thioxanthene, xanthene, ketone, thiopyrylium salt, base styryl,
merocyanine, 3-substituted coumarin, cyanine, acridine and thiazine
coloring matters, and the like. "Mutual action" herein referred to
includes movement of energy and electrons from a exited spectral
sensitizer to a polymer to be produced and/or a photopolymerization
initiator, and the like.

[0169]Next, one embodiment of the method for producing a polymer of the
present invention will be illustrated referring to drawings. FIG. 1 shows
a schematic constitution view of one example of a production apparatus. 1
represents a carbon dioxide bomb, 2 represents a carbon dioxide feeding
pump, 3 represents a reaction vessel capable of maintaining high
temperature and high pressure condition, 4 represents a temperature
control means, 5 represents a window for incidence of active energy ray
(for example, quartz window), 5' represents a window (for example, quartz
window), 6 represents a light source, 7 represents a pressure-reducing
valve, 8 represents a base material for permeation of active energy ray
(active energy ray permeable base material), 9 represents a magnetic
stirrer, 10 represents a stirring member (rotor). The window 5' may not
be provided.

[0170]The active energy ray permeable base material 8 is placed inside of
the window 5 allowing permeation of active energy ray provided on the
reaction vessel 3. The active energy ray permeable base material 8 is
placed so that a surface at the side of the window 5 as an incidence
surface of active energy ray is not exposed to supercritical carbon
dioxide or subcritical carbon dioxide and an exiting surface of active
energy ray is exposed to supercritical carbon dioxide or subcritical
carbon dioxide. The active energy ray permeable base material 8 may not
be placed so as to contact the window 5, and a member for disposition
such as an active energy ray permeable film and the like can also be
allowed to intervene.

[0171]A method of fixing the active energy ray permeable base material 8
is not particularly restricted, and mentioned are, for example, a method
in which a window is provided at the bottom of a concave portion of a
reaction vessel wall, and a base material is pushed into to be closely
adhered to the window, a method of installing a base material on a window
frame by a fastener, and other methods. It is also possible that a window
is endowed with removable constitution and this window is itself used as
a base material.

[0172]The base material is not particularly restricted providing it allows
permeation of active energy ray, and mentioned are, for example,
transparent resins or translucent resins, transparent or translucent
glass, metal oxides such as ITO (indium-tin oxide) and the like, metals
and the like. The material of the base material is selected taking the
composition of a polymer to be formed, and the like into consideration.
For example, when a bismaleimide-based polymer is formed, the polymer to
be formed shows low close adherence and can be peeled easily providing
the base material is quartz glass. On the other hand, when the base
material is a PET (polyethylene terephthalate) film, a polymer of high
close adherence is formed. For example, a base material coated with a
coating material such as polyvinyl alcohol (PVA) and the like can also be
used.

[0173]A base material made into any shape can be used. A polymerization
precursor dissolved in a supercritical fluid or subcritical fluid is
polymerized under condition of uniform distribution on the interface of
the base material, to produced a polymer having juts. Therefore, a
polymer having juts can be formed uniformly even on a base material
having a fine irregular structure or a deep irregular structure.

[0174]The window 5 for incidence of active energy ray on which the base
material 8 is placed, or a member for disposition placed thereon can have
a shape determined depending on the shape of a base material on which a
polymer having juts is formed or the shape of a desired polymer having
juts.

[0175]After placing the active energy ray permeable base material 8 in the
reaction vessel 3, a polymerization precursor and if necessary, an
additive component and a photopolymerization initiator are placed in the
reaction vessel 3. When the polymerization precursor and additive
component are in the form of liquid, the polymerization precursor,
additive component and photopolymerization initiator can also be fed from
their storage vessels by a pump into the reaction vessel 3. When two or
more polymerization precursors are used or a polymerization precursor and
an additive component are used, they can be mixed previously before
feeding to the reaction vessel 3, or they can be separately fed to the
reaction vessel 3. The polymerization precursor, additive component and
photopolymerization initiator can also be controlled at polymerization
temperature previously by a heater before feeding to the reaction vessel
3.

[0176]On the other hand, carbon dioxide is fed from the carbon dioxide
bomb 1 to the reaction vessel 3 by the pump 2. Carbon dioxide can also be
controlled at polymerization temperature previously by a heater before
feeding to the reaction vessel 3.

[0177]Pressure in the reaction vessel 3 is controlled at polymerization
pressure by the amount of carbon dioxide to be fed. On the other hand,
temperature in the reaction vessel 3 is controlled at polymerization
temperature by the temperature control means 4 such as a heater and the
like. Control of pressure in the reaction vessel 3 and control of
temperature in the reaction vessel 3 can be conducted simultaneously,
alternatively, either one can be controlled before controlling of
another.

[0178]When a polymerization precursor controlled previously at
polymerization temperature or higher temperatures by a heater and, if
necessary, an additive component and carbon dioxide are fed to the
reaction vessel 3, the temperature control means 4 such as a heater and
the like may no be provided providing temperature in the reaction vessel
3 can be kept at polymerization temperature.

[0179]After attaining given pressure and temperature in the reaction
vessel 3, active energy ray is irradiated from the light source 6 into
the reaction vessel 3 through the active energy ray permeable window 5
and the base material 8 while stirring the content of the reaction vessel
by the magnetic stirrer 9 and the stirring member 10, to cause a
photopolymerization reaction, forming a polymer having juts on an active
energy ray exiting surface of the active energy ray permeable base
material. Irradiation with active energy ray may be carried out
continuously or intermittently. It is possible to control the height of a
jut on a polymer having juts to be formed by controlling the dose of
active energy ray.

[0180]The polymer having juts to be formed by photopolymerization in the
presence of an additive component contains the additive component
selectively in the jut.

[0181]During polymerization, further, a polymerization precursor and/or an
additive component can also be fed to the reaction vessel 3. By thus
varying the composition of a polymerization precursor to be polymerized
and an additive component, the composition of resulting polymer having
juts can be changed along a direction vertical to the surface of a base
material

[0182]The stirring means used for stirring the content of a reaction
vessel is not limited to the magnetic stirrer 9 and the stirring member
10.

[0183]According to the present invention, a polymer having juts can be
formed selectively on a part on a base material through which active
energy ray permeates. For example, by irradiation with active energy ray
via a mask pattern, a polymer having juts having a desired pattern can be
formed. In this case, for example, a mask pattern may be pasted on the
outside of the window 5, or the shape itself of the window may be made
into given pattern shape.

[0184]When laser beam is used as the light source, a light irradiation
region can be narrowed as compared with other light sources, thus, a
polymer having juts having a fine pattern can be formed. Further, when
laser beam is used as the light source, light of higher intensity can be
irradiated as compared with other light sources, thus, the aspect ratio
(ratio of height to diameter of jut) and density of a jut on a polymer
having juts can be controlled more easily.

[0185]After completion of the polymerization reaction, carbon dioxide is
discharged from the pressure reducing valve 7, to decrease the pressure
in the reaction vessel 3 down to about atmospheric pressure. For
obtaining a polymer of higher purity by removing the unreacted
polymerization precursor and the like, the pressure in the reaction
vessel 3 may also be lowered to a pressure below atmospheric pressure,
for example, to a vacuum of 133 Pa or less, before returning to about
atmospheric pressure. After returning the temperature in the reaction
vessel 3 to about normal temperature, the base material 8 carrying a
formed polymer having juts is removed from the reaction vessel 3.

[0186]After completion of the polymerization reaction, high pressure under
supercritical condition or subcritical condition can be lowered quickly
or high temperature and high pressure can be lowered quickly, to foam the
polymer produced. Since a supercritical fluid or subcritical fluid has a
strong permeating force into a polymer and is uniform, a uniform porous
body can be formed by performing such treatment.

[0187]In this procedure, the polymer cooling rate and the polymer
pressure-reducing rate can be appropriately determined. By controlling
the polymer cooling rate and the polymer pressure-reducing rate, pore
diameter can be controlled. When the polymer cooling rate and the polymer
pressure-reducing rate are larger, pore diameter tends to increase.

[0188]It may also be permissible that, after polymerization, a polymer is
left if necessary in a supercritical fluid or subcritical fluid for given
time, then, quick pressure reduction or quick cooling and quick pressure
reduction is performed to foam the polymer.

[0189]The polymer having juts formed on the base material removed from the
reaction vessel 3 can also be post-cured by irradiation with
electromagnetic wave, irradiation with light or heating, or a combination
thereof.

[0190]Carbon dioxide discharged from the reaction vessel 3 after
completion of the polymerization reaction can be recovered and recycled.

[0191]The polymerization process above is shown in batch mode, however,
the polymerization can be carried out also in continuous mode or
semi-continuous mode.

[0192]The shape of the reaction vessel used for carrying out the method
for producing a polymer of the present invention is not limited to that
shown in FIG. 1. For example, it is also possible that an optical system
such as an optical fiber and the like is inserted in the reaction vessel,
and the content of the reaction vessel is irradiated with active energy
ray through this optical system.

[0193]FIG. 2 shows a schematic constitution view of another example of a
production apparatus used for carrying out the production method of the
present invention. 1 to 10 represent the same members as shown in FIG. 1.
11 and 11' represent a storage portion with an open-closeable lid for
storing a polymerization precursor and/or additive component, 12 and 12'
represent a stirring member (rotor), and 13 and 13' represent a magnetic
stirrer. A window 5' may not be provided. If necessary, only one storage
portion for a polymerization precursor and/or additive component may be
provided, or three or more such storage portions may be provided.

[0194]The storage portions 11 and 11' for a polymerization precursor
and/or additive component may have a temperature controlling means. The
stirring means for stirring the content of the storage portions 11 and
11' is not limited to the magnetic stirrers 13, 13' and the stirring
members 12, 12'. The storage portions 11 and 11' for a polymerization
precursor and/or additive component may have no stirring means for
stirring its content.

[0195]The production apparatus shown in FIG. 2 has the same constitution
as the production apparatus shown in FIG. 1 except that the storage
portions 11 and 11' with an open-closeable lid for storing a
polymerization precursor and/or additive component, the stirring members
12 and 12' for stirring the content of the storage portions 11 and 11',
and the magnetic stirrers 13 and 13' are provided.

[0196]When a polymer having juts is produced by the production apparatus
shown in FIG. 2, all of a polymerization precursor to be polymerized, and
an additive component and a photopolymerization initiator used if
necessary are not charged in the reaction vessel 3, a part of them or all
of them are charged in the storage portions 11 and 11'. In the storage
portions 11 and 11', one kind of polymerization precursor or additive
component may be charged, or two or more polymerization precursors and/or
additive components may be charged in admixture.

[0197]Before initiation of polymerization or during polymerization, if
necessary, the lid of the storage portion is opened, and a polymerization
precursor and/or additive component stored inside is fed to the reaction
vessel 3. By this, the amount and composition of a polymerization
precursor and additive component present in the reaction vessel 3 can be
controlled easily during polymerization. The polymerization precursor
and/or additive component can also be controlled at polymerization
temperature previously by a heater before feeding to the reaction vessel
3.

[0198]A polymer having juts can be produced by the same manner as in the
case of producing a polymer by the production apparatus shown in FIG. 1
described above, excepting the above-mentioned procedure.

[0199]The storage portions 11 and 11' for a polymerization precursor
and/or additive component may be equipped with no lid providing they have
a constitution in which a polymerization precursor and/or additive
component stored inside can be fed to the reaction system only when
required. For example, when the polymerization precursor and/or additive
component to be stored is not dissolved or dispersed in a supercritical
fluid or a subcritical fluid unless higher temperature is prepared, it
may be permissible that the storage portion is not equipped with a lid
and a heating means for heating the storage portion is provided.

[0200]The production apparatus shown in FIG. 2 is used particularly
suitably when the composition of the resulting polymer having juts is
changed along a direction vertical to the surface of a base material by
varying the composition of a polymerization precursor to be polymerized
and an additive component to be contained.

[0201]Thus, the polymer having juts of the present invention can be
produced. In the present invention, a polymer grows along the irradiation
direction with active energy ray, to form a jut of the polymer. Namely,
usually, a polymer grows along a direction vertical to the surface of a
base material, to form a jut of the polymer. Usually, when the
irradiation time with active energy ray (polymerization time) is longer,
the produced polymer tends to form a continuous membrane made of the
polymer having juts.

[0202]According to the present invention, a polymer having juts of which
height is 0.1-fold or more of its diameter, further, a polymer having
juts of which height is 1-fold or more of its diameter, further, a
polymer having juts of which height is 2-fold or more of its diameter,
further, a polymer having juts of which height is 3-fold or more of its
diameter, further, a polymer having juts of which height is 5-fold or
more of its diameter, can be produced. The upper limit of the ratio of
the height to the diameter of a jut is not particularly restricted, and
for example, the height of a jut can be 50-fold or more of the diameter.

[0203]According to the present invention, a polymer having juts of which
height is 10 nm or more, further, a polymer having juts of which height
is 0.5 μm or more, further, a polymer having juts of which height is 1
μm or more, further, a polymer having juts of which height is 5 μm
or more, further, a polymer having juts of which height is 10 μm or
more, further, a polymer having juts of which height is 30 μm or more,
further, a polymer having juts of which height is 50 μm or more, can
be produced. The upper limit of the height of a jut is not particularly
restricted, for example, the height of a jut can be 500 μm.

[0204]The height of a jut of a polymer can be controlled by the dose
(accumulated light quantity) of active energy ray. The height of a jut of
a polymer is in approximate proportion to the dose of active energy ray,
and when the dose of active energy ray reaches constant quantity or more,
the height of a jut of a polymer does not increase more, and interval
between juts tends to become smaller to form a continuous membrane.

[0205]Particularly, according to the present invention, a polymer having
juts of which height is 0.1-fold or more of its diameter and of which
height is 10 nm or more, further, a polymer having juts of which height
is 1-fold or more of its diameter and of which height is 1 μm or more,
further, a polymer having juts of which height is 5-fold or more of its
diameter and of which height is 50 μm or more, can be produced. A
polymer having juts of which height is larger as compared with diameter
and of which height is larger as described above cannot conventionally be
obtained by polymerizing a polymerization precursor such as a monomer and
the like.

[0206]The surface density of a jut of a polymer having juts is not
particularly restricted, and according to the present invention, for
example, a polymer having juts of which surface density is as high as
0.01/nm2 or more, further, 0.1/nm2 or more can be formed on a
base material. The density of a jut of a polymer having juts can also be
lowered, and the surface density of a jut can be, for example,
0.001/μm2.

[0207]Here, when the polymer having juts is a polymer in the form of
projection, the surface density of a jut means the density of a polymer
in the form of projection on the surface of a base material.

[0208]According to the present invention, a polymer having juts can be
formed on a base material together with the polymerization. The
polymerization precursor to be polymerized and additive component can be
appropriately selected, and in addition, the resulting polymer having
juts contains a jut of which height is larger as compared with diameter
and of which height is larger.

[0209]As described above, a polymer having juts to be formed can be easily
peeled from a base material depending on the base material to be
selected, therefore, for example, it can also be obtained as a resin film
having at least one projection containing at least one additive
component.

[0210]Further, in the present invention, it is also possible to change the
composition of the resulting polymer having juts along a direction
vertical to the surface of a base material by varying the composition of
a polymerization precursor to be polymerized and an additive component to
be contained or by varying at least one of pressure and temperature
during polymerization.

[0211]As described above, according to the present invention, for example,
a polymer having juts containing various additive components can be
obtained. Additionally, the resulting polymer having juts contains a jut
of which height is larger as compared with diameter and of which height
is larger. Further, a polymer having juts of which composition varies
along a direction vertical to the surface of a base material can also be
obtained.

[0212]Thus, according to the present invention, a polymer having juts
having various physical properties and functions can be obtained. The
polymer having juts of the present invention is, particularly because of
its peculiar form, expected to be applied to various uses, and a novel
functional structure is also expected to be realized.

[0213]For example, a polymer having juts containing an organopalladium
complex as the additive component can be used for electroless plating of
Ni and the like. The combination of an additive component (organometal
complex) and a metal to be plated is not limited to a combination of an
organopalladium complex and Ni, and appropriately determined.

[0214]Further, for example, a drug in the form of particle can be produced
by using various medicinal components as the additive component.

[0215]Further, the polymer having juts of the present invention can be
applied to artificial organs such as artificial kidney, artificial lung
and the like, and plasma purifying materials and the like by
appropriately selecting a polymerization precursor to be polymerized and
if necessary, an additive component, utilizing its peculiar form.

[0216]A polymer having juts containing an organometal complex such as an
organoplatinum complex and the like as the additive component can also be
calcined for metallization, to form a metal membrane having a specific
fine structure (including also metal oxide membrane). The metal membrane
after calcination maintains approximately the shape of the polymer having
juts containing an organometal complex before calcination, and has a
porous structure.

[0217]The calcination conditions for forming a metal membrane can be
appropriately determined depending on the kind of an organometal complex
as the additive component, and the like. For example, a metal membrane
can be formed by calcining a polymer having juts containing an
organometal complex in an oxygen-containing gas such as air and the like
at 250 to 2000° C. for 5 minutes to 48 hours. Usually, the
calcination temperature is preferably 300° C. or more, and
preferably 1700° C. or less. On the other hand, the calcination
time is preferably 10 minutes or more and preferably 5 hours or less.

[0218]Thus obtained metal membrane is also be expected to be applied to
various uses. For example, a titanium oxide membrane, or a membrane
composed of titanium oxide and a noble metal such as platinum and the
like, obtained by the pre-sent invention, is expected to be used as a
photo-catalyst of high activity, particularly, as a photo-catalyst of
high activity for purifying environments.

[0219]Further, a polymer having juts containing a metal and/or metal oxide
can also be formed by reducing a polymer having juts containing an
organometal complex such as an organoplatinum complex, organopalladium
complex and the like as the additive component to convert the organometal
complex into a metal, and depending on the metal, into a metal oxide.

[0220]The reducing treatment method and reducing treatment conditions for
forming a polymer having juts containing a metal and/or metal oxide are
not particularly restricted, and can be appropriately determined
depending on the kind of an organometal complex as the additive
component.

[0221]Examples of the reducing treatment method include a method in which
a polymer having juts containing an organometal complex is immersed in a
solution containing a reducing agent, a method in which a polymer having
juts containing an organometal complex is allowed to contact a reducing
gas to cause gas phase reduction, and other methods.

[0222]In the method of immersing a polymer having juts containing an
organometal complex into a solution containing a reducing agent, the
reducing agent to be used is not particularly restricted providing it can
reduce an organometal complex as the additive component into a metal or a
metal oxide. Examples of the reducing agent include sodium borohydride,
potassium borohydride, dimethylamineborane (DMAB), trimethylamineborane
(TMAB), hydrazine, formaldehyde, derivatives of these compounds, sulfites
such as sodium sulfite, hypophosphites such as sodium hypophosphite and
the like. As the reducing agent, also mentioned are ferrous salts such as
FeSO4 and the like, metal hydrogen phosphates such as sodium
hypophosphite and the like, hydroxylamine sulfate, hydrosulfite and the
like.

[0223]The solvent containing a reducing agent is usually an aqueous
solution, and the solvent for dissolving a reducing agent is not limited
to water. Examples of the solvent for dissolving a reducing agent include
methanol, ethanol, ethyl ether, hexane, benzene, methylene chloride,
diglyme (diethylene glycol dimethyl ether), tetrahydrofuran,
dimethylacetamide, dimethyl sulfoxide, acetonitrile and the like.

[0224]The concentration of a reducing agent in a solution containing the
reducing agent is usually about 0.003 to 0.1 mol/liter. When the
concentration of a reducing agent in a solution containing the reducing
agent is 0.003 mol/liter or more, the speed of the reducing reaction
becomes sufficiently large. The concentration of a reducing agent in a
solution containing the reducing agent is preferably 0.005 mol/liter or
more. On the other hand, when the concentration of a reducing agent in a
solution containing the reducing agent 0.1 mol/liter or less, falling of
the deposited metal can be suppressed sufficiently.

[0225]Usually, the reducing treatment temperature may advantageously be
about 20 to 90° C. The reducing treatment temperature is
preferably 25° C. or more, and preferably 80° C. or less.
Usually, the reducing treatment time may be advantageously about 1 to 10
minutes. The reducing treatment time is preferably 2 minutes or more and
preferably 5 minutes or less.

[0226]In the method of allowing a polymer having juts containing an
organometal complex to contact a reducing gas to cause gas phase
reduction, the reducing gas to be used is not particularly restricted
providing it can reduce an organometal complex as the additive component
into a metal or a metal oxide. Examples of the reducing gas include a
hydrogen gas, diborane gas and the like.

[0227]The reducing treatment conditions such as the reducing treatment
temperature, reducing treatment time and the like can be appropriately
determined depending on the kind of a reducing gas to be used, the kind
of an organometal complex as the additive component, and the like. For
example, when a hydrogen gas is used as the reducing gas, it may be
advantageous to effect treatment at temperatures of about 30 to
300° C. for about 5 to 60 minutes in a hydrogen gas flow.

[0228]The reducing treatment temperature may be appropriately determined
taking the heat resistance of a polymer to be treated and a base
material, reducing tendency of an organometal complex as the additive
component, and the like into consideration.

[0229]The reducing treatment is usually carried out until an organometal
complex present at least on the surface of a polymer is reduced
approximately completely, and if necessary, the reducing treatment may be
stopped on the way before complete reduction.

[0230]Thus obtained polymer having juts containing a metal and/or metal
oxide can be used, for example, as a plating bed.

[0231]According to the present invention, it is possible for form a
polymer having juts containing an additive component uniformly even on a
base material having a fine irregular structure or a deep irregular
structure. For example, according to the present invention, it is also
possible to coat the inside of a fine reaction vessel having a diameter
of decades μm called micro reactor.

[0232]Further, according to the present invention, it is possible to form
a polymer having juts containing an additive component selectively on a
part of an active energy ray exiting surface of a base material through
which active energy ray has permeated. Therefore, it is possible to form
a polymer having juts containing an additive component having a given
fine pattern.

[0233]The polymer having juts of specific size of the present invention
has, because of its peculiar form, an excellent water-repellant function.
For example, it is possible to obtain a polymer having juts having
extremely high water-repellency (super water-repellency) showing a
contact angle with water of 90° or more, further, 100° or
more. The contact angle with water is obtained by dropping one drop (15
μl) of pure water on the surface of a polymer membrane as a measuring
subject at a measuring temperature of 20° C., and 10 seconds after
dropping, measuring the contact angle of the water drop with the polymer
membrane by observing the shape of the water drop by a microscope and the
like.

[0234]The polymer (membrane) having such excellent water-repellency is
used widely in window panes of automobiles, ships, aircrafts and the
like, kitchen equipments, kitchen goods, bath equipments, lavatory
equipments, mirrors, parabola antennae, other fields since it can repel
water and oil and easily remove substances adhered to its surface.

[0235]The water-repellent function of the polymer having juts of the
present invention is ascribable to its peculiar form. Namely, the polymer
having juts of the present invention ha high water-repellency
irrespective of the composition of the polymer. Therefore, according to
the present invention, a polymer (membrane) having a composition suitable
for its use can be endowed with an excellent water-repellent function.

[0236]The polymer having juts of the present invention has, because of its
peculiar form, also an excellent sticky function. The polymer having juts
of the present invention can be used in various fields as a sticky agent
or a sticky sheet.

[0237]Further, the polymer having juts of the present invention has also
an excellent adsorption function. The polymer having juts of the present
invention can be used in various fields as an adsorption agent or a
separation membrane (gas separation membrane and the like).

[0238]More specifically, the polymer having juts of the present invention
can be used, utilizing its peculiar form, for detection and selection of
DNA (DNA sensor) by appropriately selecting a polymerization precursor to
be polymerized.

[0239]The polymer having juts of the present invention can also be applied
to backlight guiding and scattering plates of displays by appropriately
selecting a polymerization precursor to be polymerized.

[0240]Further, a metal membrane can also be formed on the polymer having
juts of the present invention by known methods such as vapor deposition,
plating and the like. The metal membrane is not limited to a metal single
body, and may be an alloy, and may also be a metal oxide, metal nitride,
metal carbide or the like.

[0241]A product obtained by forming a metal membrane or metal oxide
membrane on the polymer haying juts of the present invention can be
applied to an electron gun and the like. This electron guns can be used,
for example, for a display and the like.

[0242]It is also possible that a metal membrane is peeled from the polymer
having juts of the present invention by a known method, and resulting
metal membrane is used as a mold for resin extrusion molding.

[0243]Further, according to the present invention, a polymer having juts
can be formed uniformly even on a base material having a fine irregular
structure or a deep irregular structure. For example, according to the
present invention, it is also possible to coat the inside of a fine
reaction vessel having a diameter of decades μm called micro reactor.

[0244]It is also possible to form a polymer having juts in which nano
particles or other additives are uniformly dispersed, and for example, a
colored membrane and a fluorescent membrane can also be formed.

[0245]The following examples will illustrate the present invention further
in detail. The present invention is not limited to these examples.

EXAMPLE 1

[0246]Into a pressure-resistant reaction vessel having a content volume of
30 cm3 having a quartz pressure-resistant window at the bottom of a
concave portion provided on the inside wall of the reaction vessel was
charged 0.872 g of polyether bismaleimide acetate (manufactured by
Dainippon Ink & Chemicals. Inc., MIA-200) as a polymerization precursor
and 0.026 g of an organoplatinum complex
[1,5-cyclooctadiene)dimethylplatinum (II)] as an additive component.
Next, carbon dioxide was introduced into the reaction vessel at a bomb
pressure of about 7 MPa while stirring the content of the reaction
vessel, then, the temperature was raised to 35° C., further,
carbon dioxide was introduced by a pressure pump so that the pressure in
the reaction vessel was 30 MPa, to give supercritical condition. The
charging concentration of the polymerization precursor polyether
bismaleimide acetate was 3.5 wt %.

[0247]After stirring at a pressure of 30 MPa and a temperature of
35° C. for 1 hour, then, ultraviolet ray was irradiated from
outside of the reaction vessel through the quartz pressure-resistant
window into the reaction vessel at a dose of 10 J/cm2 using an
extra-high pressure mercury lamp equipped with quartz fiber as a light
source. The conditions for irradiation with ultraviolet ray in this
operation included an irradiation intensity of 33 mW/cm2 and an
irradiation time of 303 seconds. The wavelength of the irradiated
ultraviolet ray was in a range from 254 to 436 nm. As a result, on the
quartz pressure-resistant window, a polymer was formed having juts grown
along the ultraviolet ray irradiation direction, namely, a direction
vertical to the surface of the base material.

[0248]After irradiation with ultraviolet ray, carbon dioxide was
discharged out of the reaction vessel gradually over a period of 120
minutes, to reduce the pressure in the reaction vessel down to
atmospheric pressure.

[0249]By XMA (X-ray micro analyzer), the Pt surface of the resulting
polymer having juts was analyzer. The SEM photograph (upper view) and XMA
Pt image (lower view) of the resulting polymer having juts are shown in
FIG. 3. In the lower view, XMA Pt image, in FIG. 3, a white portion shows
Pt. As a result, it was found that, in the polymer having juts, the jut
had high Pt concentration. That is, it was found that a polymer having
juts containing an organoplatinum complex as an additive component was
formed.

[0250]The resulting polymer having juts was calcined at 450° C. for
5 hours in air to metallize Pt. The SEM photograph of the resulting metal
Pt membrane is shown in FIG. 4. The metal Pt membrane after calcination
maintained the shape of the polymer having juts containing an
organoplatinum complex before calcination, and it was porous.

EXAMPLE 2

[0251]Photopolymerization was carried out in the same manner as in Example
1 except that a mask pattern was pasted on the outside of the quartz
pressure-resistant window and ultraviolet ray was irradiated via this
mask pattern into the reaction vessel. As a result, a polymer having juts
containing an organoplatinum complex was formed in which the mask pattern
was transferred to a part on the quartz pressure-resistant window through
which ultraviolet ray had been permeated.

EXAMPLE 3

[0252]Photopolymerization was carried out in the same manner as in Example
1 to obtain a polymer having juts containing an organoplatinum complex as
an additive component.

[0253]The resulting polymer having juts was immersed in a 0.3% NaBH4
aqueous solution at room temperature, to effect reduction treatment.
About 2 minutes after immersion in a 0.3% NaBH4 aqueous solution,
metal platinum was deposited on the surface of the polymer having juts.

EXAMPLE 4

[0254]Photopolymerization was carried out in the same manner as in Example
1 except that the additive component was an organopalladium complex
(palladium acetate), to obtain a polymer having juts containing an
organopalladium complex as an additive component.

[0255]The resulting polymer having juts was immersed in a 0.3% NaBH4
aqueous solution at room temperature, to effect reduction treatment.
After washing with pure water, this polymer having juts was immersed in
concentrated sulfuric acid (concentration: 50 mL/L) while stirring at
40° C. (313K) for 2 minutes, to effect catalyst activation for
plating. This polymer having juts was removed out of concentrated
sulfuric acid, and washed with pure water.

[0256]Next, into a 5 L beaker was placed an aqueous solution for
electroless copper plating [mixed aqueous solution of OPC700A
(concentration: 100 mL/L) manufactured by Okuno Seiyaku Kogyo and OPC700B
(concentration: 100 mL/L) manufactured by Okuno Seiyaku Kogyo], and the
above-mentioned polymer having juts was immersed in this aqueous solution
for electroless copper plating while stirring and bubbling air into the
vessel at room temperature for 60 minutes, to effect copper plating
treatment. This polymer having juts was removed out of the aqueous
solution for electroless copper plating and washed with pure water.

[0257]Subsequently, into a 5 L beaker was placed an aqueous solution for
electroless copper plating [mixed aqueous solution of OPC copper Ti
(concentration: 60 mL/L) manufactured by Okuno Seiyaku Kogyo, OPC copper
T2 (concentration: 12 mL/L) manufactured by Okuno Seiyaku Kogyo and OPC
copper T3 (concentration: 100 mL/L) manufactured by Okuno Seiyaku Kogyo],
and the above-mentioned polymer having juts was immersed in this aqueous
solution for electroless copper plating while stirring and bubbling air
into the vessel at 60° C. (333K) for 120 minutes, to effect copper
plating treatment. This polymer having juts was removed out of the
aqueous solution for electroless copper plating and washed under
ultrasonic in pure water for 5 minutes and in methanol for 10 minutes.

[0258]On the polymer having juts thus subjected to copper plating
treatment, apparently, a uniform plating membrane with no swelling
(thickness of plating layer; 2 μm) was formed on the surface of the
polymer.

EXAMPLE 5

[0259]Into a pressure-resistant reaction vessel having a content volume of
30 cm3 having a quartz pressure-resistant window at the bottom of a
concave portion provided on the inside wall of the reaction vessel was
charged 0.872 g of polyether bismaleimide acetate (manufactured by
Dainippon Ink & Chemicals. Inc., MIA-200) as a polymerization precursor.
Next, carbon dioxide was introduced into the reaction vessel at a bomb
pressure of about 7 MPa while stirring the content of the reaction
vessel, then, the temperature was raised to 35° C., further,
carbon dioxide was introduced by a pressure pump so that the pressure in
the reaction vessel was 30 MPa, to give supercritical condition. The
charging concentration of the polymerization precursor polyether
bismaleimide acetate was 3.5 wt %.

[0260]After stirring at a pressure of 30 MPa and a temperature of
35° C. for 1 hour, then, ultraviolet ray was irradiated from
outside of the reaction vessel through the quartz pressure-resistant
window into the reaction vessel at a dose of 1 J/cm2 using an
extra-high pressure mercury lamp equipped with quartz fiber as a light
source. The conditions for irradiation with ultraviolet ray in this
operation included an irradiation intensity of 33 mW/cm2 and an
irradiation time of 30.3 seconds. The wavelength of the irradiated
ultraviolet ray was in a range from 254 to 436 nm. As a result, on the
quartz pressure-resistant window, a polymer was formed having juts grown
along the ultraviolet ray irradiation direction, namely, a direction
vertical to the surface of the base material.

[0261]After irradiation with ultraviolet ray, carbon dioxide was
discharged out of the reaction vessel gradually over a period of 120
minutes, to reduce the pressure in the reaction vessel down to
atmospheric pressure. The SEM photograph of the resulting polymer having
juts is shown in FIG. 5.

EXAMPLE 6

[0262]Photopolymerization was carried out in the same manner as in Example
5 except that the conditions for irradiation with ultraviolet ray
included an irradiation intensity of 33 mW/cm2, an irradiation time
of 152 seconds and a dose of 5 J/cm2. As a result, on the quartz
pressure-resistant window, a polymer was formed having juts grown along
the ultraviolet ray irradiation direction, namely, a direction vertical
to the surface of the base material. The SEM photograph of the resulting
polymer having juts is shown in FIG. 6.

EXAMPLE 7

[0263]Photopolymerization was carried out in the same manner as in Example
5 except that the conditions for irradiation with ultraviolet ray
included an irradiation intensity of 33 mW/cm2, an irradiation time
of 303 seconds and a dose of 10 J/cm2. As a result, on the quartz
pressure-resistant window, a polymer was formed having juts grown along
the ultraviolet ray irradiation direction, namely, a direction vertical
to the surface of the base material. The SEM photograph of the resulting
polymer having juts is shown in FIG. 7.

[0264]The contact angle with water of the resulting polymer having juts
was measured by dropping one drop (15 μl) of pure water on the surface
of a polymer membrane, and 10 seconds after dropping, measuring the
contact angle of the water drop with the polymer membrane by observing
the shape of the water drop, using a contact angle measuring apparatus
CA-X150 manufactured by Kyowa Kaimen Kagaku under conditions of a
temperature of 20° C. and a humidity of 55%. As a result, the
contact angle with water of the resulting polymer having juts was 109.90.
On the other hand, a continuous membrane obtained by polymerizing the
same polymerization precursor (manufactured by Dainippon Ink & Chemicals.
Inc., MIA-200) showed a contact angle with water of 90°. The
polymer having juts of the present invention had higher water-repellency
as compared with the continuous membrane of the same composition. The
water-repellency of the resulting polymer having juts was equivalent to
that of PTFE (polytetraflyoroethylene).

EXAMPLE 8

[0265]Photopolymerization was carried out in the same manner as in Example
7 except that a mask pattern was pasted on the outside of the quartz
pressure-resistant window and ultraviolet ray was irradiated via this
mask pattern into the reaction vessel. As a result, a polymer having juts
was formed in which the mask pattern was transferred to a part on the
quartz pressure-resistant window through which ultraviolet ray had been
permeated.

REFERENCE EXAMPLE 1

[0266]Photopolymerization was carried out in the same manner as in Example
5 except that the conditions for irradiation with ultraviolet ray
included an irradiation intensity of 33 mW/cm2, an irradiation time
of 1515 seconds and a dose of 50 J/cm2. As a result, on the quartz
pressure-resistant window, a polymer membrane was formed.

[0267]The SEM photograph of the resulting polymer membrane is shown in
FIG. 8. The schematic sectional view of the resulting polymer membrane is
shown in FIG. 9. 21 represents a base material (quartz pressure-resistant
window) and 22 represents a polymer membrane. The polymer membrane
obtained in Reference Example 1 showed progress of formation of a porous
continuous membrane as compared with the polymer having juts obtained in
Example 7.

[0268]In Examples 5 to 7, the size of the jut is as shown in FIGS. 5 to 7,
and specifically, the height of the jut was about 0.5 to about 100 μm,
the height of each jut was about 0.1 to about 10-fold of the each
diameter.

INDUSTRIAL APPLICABILITY

[0269]According to the present invention, a polymer having juts having
various physical properties and functions, and a membrane containing as
the main component a metal and/or metal oxide having a specific fine
structure, can be obtained. For example, application to various uses such
a medical materials, pharmaceutical materials, separation function
materials, sensor materials, catalyst materials and the like is expected.
Further, realization of a novel functional structure is also expected.

[0270]Furthermore, according to the present invention, a polymer having
juts of which height is larger as compared with its diameter and of which
height is large can be obtained, and application to various used such as,
for example, water-repellent materials, sticky materials, adsorption
materials, separation function materials, sensor materials, display
materials, medical materials and the like is expected. Further,
realization of a novel functional structure is also expected.